Process of preparing diphenyl derivatives



Patented 19, 1935 I UNITED STATES PROCESS or ran DERIV Robert L. Sibley,Nitro,

W. Va., assignor to Rubber Service Laboratories Company, Akron, Ohio,'acorporation of Ohio No Drawing. Original application September 26,

1932, Serial No. plication October 22,

Claims.

The present invention relates to new com-- pounds for increasing thewetting, penetrating and cleansing'capacity of treatment liquids,particularly such as are employed in the textile,

6 leather andrubber industries.

In general such liquids are efiective largely on account of their effecton the interfacial tension between water andan oily or greasy surface.It

is generally conceded that liquids having the greater surface tensionhave the least wettingout power.

According to the present invention anew class of compounds has beendiscovered which possess to a large degree the property of reducing thesurface tension of aqueous solutions, and which have been found topossess exceptional wetting, penetrating and cleansing properties.

The new class of materials possessing these desirable wetting,penetrating and cleansing properties comprise the sulphuric acidderivatives of the reaction products of an alcohol and a hydroxysubstituted diphenyl or a salt thereof as, for example an alkali orammonium salt.

The-following example illustrates one method by which thepreferred'class of materials was prepared.

7 Example I 907 grams of a mixture of substantially 85% of ortho hydroxydiphenyl and 15% of para hydroxy diphenyl and 800 grams of normal butylalcohol (the quantities ofthe hydroxy diphenyl and butyl alcoholemployed above are in the ratio of substantially one molecularproportionof hydroxy diphenyl to a slight excess over two'molecular proportions ofbutyl alcohol) were placed in a. suitable reactor equipped with a refluxcondenser and heated at refluxing temperature for substantially twohours. The reaction product so obtained was then allowed to cool tosubstan-- tially 0.", after which 4000 grams of 93% sul-' phuric acidwas added slowly thereto at a tem--v perature of substantially 75 to 85C. After the addition of the sulphuric acid was completed, the resultingproduct was heated for a period of substantiallyfour hours at atemperature of substantially to C. The product thus obtained was in theform of two layers, the upper layer of which was drawnv ofl and dilutedwith water to a volume having a total weight of substantially 6000grams. The charge r was then heated to to 95 C. and treated withsuflicient freshly slaked lime to convert the free sulphuric acidpresent to calcium sulphate and to convert the sulphuric acid,derivative of the reaction Divided and this Mb- 1932, Serial No. 639,149

substituted diphenyl to they calcium salt thereof. After filtering offthe calcium sulphate formed by the liming treatment described,suflicient sodium carbonate, preferably as a concentrated solutionthereof, was added to the filtrate to convert" the calcium salt of theabove described reaction product to the corresponding sodium salt. Thecalcium carbonate thereby precipitated was filtered oil and the filtratecomprising an aqueous solution of one of the preferred materials, whichmay product of normal butyl alcohol and hydroxy be called the sodiumsalt of the sulfonated normal butylated ortho-para hydroxy diphenyl,may, if desirable, be employed as a wetting, penetrating or cleansingagent according to the present invention, or if preferred the aqueoussolution thereof may be partially concentrated or completely dried andemployed in the form of a solid. Furthermore, other soluble salts thanthe sodium salt, for example, the potassium salt may be prepared andemployed in the process accordingto the present invention. Again, thefree sulphuric acid derivative described above has been neutralizeddirect with aqueous sodium hydroxide solution, thus simplifying the morecomplicated lime and soda ash method.

' In order to show the wetting and penetrating effect of the new andpreferred class of materials the following test was employed. A bundleof cotton or wool yarn composed of sixteen strands each two inches inlength was placedon the surface of a one percent aqueous solution of thewetting or penetrating agent and the time required for the yarn to sinkbelow the surface of the liquid is known as the wetting-out time.

A test carried out in the manner described showed a one percentsolutionof the sodium saltof the sulfonated normal butylated ortho-' parahydroxy diphenyl prepared as in Example I wet wool and cotton in 1.8 and2.2 seconds respectively. A test carried out in the same manner asindicated above with the exception that there was no'wetting agent addedto the water,

cotton and wool test pieces.

- showed-substantially no wetting whatever of the As it is known thatliquids that have the greatest surface tension have the leastwetting-out power, a comparison showing the difference indi-,

cated between the surfacetension of water and that of a one percentaqueous solution of the preferred materials was made. The methodemployed was essentially that described by A. J. Hall in the TextileColorist, volume 48, (1926) pages I 809 to 812 inclusive. The apparatusemployed consisted in a pipette havingv attachedthereto a piece ofrubber tubing and a pinch clamp, and marked so as to show a volumebetween markings of 3 c. c. In comparing the surface tension of any twoliquids, one liquid is'drawn into the pipette and by adjustment of thepinch clamp is allowed to fall in drops from the lower end of thepipette at a regular rate and the number of drops which fall while thelevel of the liquid passes between the 3 c. c. markers at a temperatureof 25 C. is noted. Under similar conditions, the number of drops whichfall when the other liquid is in the pipette is also obtained. Thenassuming that the specific gravities of the two liquids are the same (a.correction can be made when this is not the case) the surface tensionsare inversely proportional to the number of drops which fall. tioncomparisons showing the differences in surface tensions of the liquidsare indicated by the number of drops which fall in the above test. Thisnumber of drops is hereinafter called the drop number.

. A one percent aqueous solution of the sodium salt of the sulphonatednormal butylated orthopara hydroxy diphenyl was found in the testhereinbefore described to possess a drop number of 144, while water wasfound to possess a drop number of 61; It is thus apparent that thepreferred class of materials possess characteristics which markedlylower the surface tension of liquids thus indicating their value aswetting and pene-' trating agents,

Other sulphuric acid derivatives, as well as the alkali salts thereof,of thereaction products of an alcohol and a hydroxy substituted diphenylthan. that set forth in Example -I have been prepared and the productsso obtained found to possess the desirable wetting out characteristicsof the class. Thus, the sodium salts of the following materials havebeen prepared in a manner analogous to that hereinbefore set forth.

A. The sulphuric acid derivative of the reaction product of iso-propylalcohol and a mixture of substantially 85% ortho and substantially-15%para hydroxy diphenyl;

B. The sulphuric acid derivative of the reaction product of normal butylalcohol and parahydroxy diphenyl.

C. The sulphuric acid derivative of the reaction product of normal butylalcohol and ortho hydroxy diphenyl. v

D. The sulphuric acid derivative of the reaction-product of iso-butylalcohol and a mixture of substantially 85% ortho and substantially 15%para hydroxy diphenyl.

E. The sulphuric acid derivative of the reaction product of normal amylalcohol and a mixture of substantially 85% ortho and substantially 15%para hydroxy diphenyl.

Testscarried out in the manner hereinbefore set forth showing thewetting-out time of one percent aqueous solutions of the above materialsare given in the following table.

In the present specificaindustries.

showed a marked lowering of the surface tension of the. liquids.

other examples of the preferred class of wet I ting, penetrating andcleansing agents that have been prepared and fall within the scope ofthe present invention comprise the free acid and the sodium salt of thesulphuric acidderivatives of the following materials: the reaction'product of cyclohexanol and a mixture of substantially '85% ortho andsubstantially 15% para hydroxy diphenyl; the reaction product of benzylalcohol and a mixture of substantially 85% ortho and substantially parahydroxy diphenyl; the' reaction product of octyl alcohol and a mixtureof substantially 85% ortho and substantially 15% para hydroxy diphenyl.

product of normal butyl alcohol and the residue obtained from thedistillation of crude phenol prepared by the benzenesulphonation-caustic The sulphuric acid derivative of the reactionfusionprocess, which residue is largely composed of hydroxy substituteddiphenyl, also was found to possess the characteristic wetting-outproperties of the preferred class of materials.

From the data hereinbefore set forth, it is read-- ily apparentthat thepreferred class of materials has marked wetting and penetratingproperties.

applicable for use in the textile,rubber and leather Tests have alsobeen carried out which demonstrated that the sulphuric acid derivativesof the reaction product of an alcohol and a hydroxy substituted diphenylpossess marked cleansing properties.

By the term hydroxy substituted diphenyl" as appearing in the presentspecification and claims is meant a compound comprising two benzenenuclei joined together through a single carbon atom of each bymeans of asingle bond, said compound containing one or more hydroxy substituents.By the term alkali metal as appearing in the present specification andclaims is meant lithium, sodium, potassium, rubidium, caesium and theammonium radical NR4.

The present application is a division of my prior application Serial No.634,929, filed September 26, 1932. What is claimed is: 1. The sulphuricacid derivatives tion products of a monohydric alcohol anda nuclearhydroxy substituted diphenyl and their alkali metal and alkalineearth-salts.

of the reac 2. An alkali metal salt ofthe sulphuric acid derivative -ofthe reaction product of a mono-. hydric alcohol and a nuclear hydroxysubstituted diphenyl.

3. An alkali metal salt of the sulphuric acid derivative of the reactionproduct of an aliphatic monohydric alcohol and a nuclear hydroxy sub-'stituted diphenyl.

4.. An alkali metal salt of-the sulphuric acid derivative of thereaction product of butyl al- 'cohol and a nuclear hydroxy substituteddi-v phenyl. v

5. An alkali metal salt of the sulphuric acid derivative of the reactionproduct of normal butyl alcohol and an ortho hydroxy substituteddiphenyl.

' 6. The'sodlum salt of the sulphuric acid derivative of the reactionproduct of normal butyl alcohol and ortho hydroxy diphenyl.

"I. The sodium salt of the sulphuric acid-dc rivative of the reactionproduct of normal butyl alcohol and a mixture of ortho and para hydroxy.diphenyl. 4

" hydroxy 'diphe'nyl and substantially 15% para hydroxy diphenyl.

9. The sodium salt of a sulphonated butylated mixture of ortho hydrondiphenyl and para hydroxy diphenyl.

10. A process for the preparation of a diphenyl. derivative comprisingreacting a nuclear hydroxy substituted diphenyl with a monohydric.alcohol and further reacting the product so formed with sulphuric acid.

11. A process for the preparation ofa diphenyl derivative comprisingheating a nuclear hydroxy substituted diphenyl with an aliphaticmonohydric alcohol and further reacting the product so formed withsulphuric acid.

12. A process for the preparation of a diphenyl derivative comprisingheating a nuclear hydroxy substituted diphenyl with butyl alcohol andfurther reacting the product so formed with sulphuric acid.

13. A process for the preparation of a diphenyl derivative comprisingheating a nuclear hydroxy substituted-diphenyl with normal butyl alcoholand further reacting the product so formed with sulphuric acid.

14. A process for the preparation of a diphenyl derivative comprisingheating orthohydroxy diphenyl with normal butyl alcohol and furtherreacting the product so formed with sulphuric acid.

15. A process for the preparation of a diphenyl derivative comprisingheating a nuclear hydroxy substitutedidiphenyl with an aliphaticmonohydric alcohol, further reacting the product so formed withsulphuric acid and isolating the diphenyl derivative thus produced asthe alka metal salt thereof.

16. A process for the preparation of a diphenylderivative comprisingheating a nuclear hydroxy substituted diphenyl with butyl alcohol,further reacting the product so formed with sulphuric. acid andisolating the diphenyl derivative thus Produced as the alkali metal saltthereof.

17. A process for the preparation of a diphenyl derivative comprisingheating normal butyl alcohol and a mixture of, ortho and para hydroxydiphenyl, further reacting the product so formed with sulphuric acid andisolating the diphenyl derivative thus produced as the alkali metal saltthereof.

19. A process for the preparation of a diphenyl derivative comprisingheating normal butyl alcohol and a mixture of substantially 85% orthohydroxy diphenyl and substantially 15% para, hydroxy diphenyl, furtherreacting the product so formed with sulphuric acid and isolating thediphenyl derivative thus produced as the sodium salt thereof.

20. A process for the preparation of a diphenyl derivative comprisingheating substantially two molecular proportions of normal butyl alcoholand substantially one molecular proportion of a mixture of substantially85% of ortho hydroxy diphenyl and substantially'15% of para hydroxydiphenyl at refluxing temperature, adding concentrated sulphuric acidthereto at a temperature of substantially to 0.. separating thesulphuric acid derivative of the reaction product of normal butylalcohol and the mixture of ortho and para hydroxy diphenyls thus formed

